N-chlorothio urea production

ABSTRACT

N-chlorothio ureas are produced by an improved process which comprises the reaction of sulfur dichloride and an urea having at least one hydrogen substituted on an urea nitrogen atom in the presence of a rate determining amount of an acid acceptor. The Nchlorothio ureas are useful intermediates in the preparation of pesticides.

United States Patent [191 Cleveland Dec. 31, 1974 N-CHLOROTHIO UREA PRODUCTION [75] Inventor: James D. Cleveland, Albany, Calif.

[73] Assignee: Chevron Research Company, San Francisco, Calif.

[22] Filed: May 8, 1972 [21] Appl. No.: 250,895

[52] US. Cl 260/545 R, 71/98, 260/470,

260/481- C, 260/553 R [51] Int. Cl. C07c 127/20 [58] Field of Search 260/545 R [56] References Cited FOREIGN PATENTS OR APPLICATIONS 2,045,440 3/1972 Germany 260/545 R Primary Examiner-Lorraine A. Weinberger Assistant Examiner-Paul J. Killos Attorney, Agent, or Firm-G. F. Magdeburger; John Stoner, Jr.; Raymond Owyang 57 ABSTRACT 9 Claims, No Drawings N-CHLOROTHIO UREA PRODUCTION DESCRIPTION OF THE PRIOR ART Processes for producing sulfenyl chloride (chlorothio) derivatives of compounds having active hydrogen atoms substituted on nitrogen are known. U.S. Ser. No. 88,105 now U.S. Pat. No. 3,679,733 and Se-r. No. 88,212, now U.S. Pat No. 3,755,437 of M. S. Brown and'G. K. Kohn, filed Nov. 9, 1970, disclose the prepration of sulfenyl halide derivatives of urea and carbamate compounds. U.S. Ser. No. 45,902 now'U.S. Pat. No.

3,623,873 ofG. K. Kohn, filed June 12, 1970, discloses the preparation of sulfenyl halide derivatives of amides. E. Kuhle, Synthesis, 573 (1970), discloses the preparation of sulfenyl halide derivatives of sulfoamides and amines.

DESCRIPTION OF THE INVENTION The N-chlorothio ureas produced by the process of the invention are represented by the formula (I):

SCI

wherein R is hydrogen or alkyl of l to 6 carbon atoms, cycloalkyl 0f3 to 10 carbon atoms, aryl of 6 to 10 carbon atoms optionally substituted 'with l to 4 halogens of atomic number 9 to 35 (fluorine, chlorine, or bromine), trihalomethyl groups wherein the halogen is fluorine or chlorine, nitro groups, or alkoxy groups individually of l to 4 carbon atoms; R and R independently are R or alkoxy of l to 4 carbon atoms such as methoxy, ethoxy, propoxy, etc. R may also be alkoxy of l to 4 carbon atoms especially methoxy.

Representative alkyl groups which R, R and R may represent include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl and n-hexyl. The preferred alkyl group is methyl.

Representative cycloalkyl groups which R, R and R may represent include monocyclic groups such as cyclopropyl, cyclopentyl, cyclohexyl, Z-methycyclohexyl, 4-methylcyclohexyl, cycloheptyl, and cyclooctyl; and bicyclic groups such as bicyclo[3-.2.0]heptyl, bicyclo[2.2.l] heptyl, bicyclo[3.3.0] octyl, bicyclo[4.2.0] octyl, bicyclo[3.3.0] octyl, and bicyclo[3.2.l] octyl. Cycloalkyl groups preferably are monocyclic groups having 5 to 6 carbon atoms.

Representative hydrocarbyl aryl groups which R, R and R may represent include phenyl; naphthyl; alkaryl of 7 to 10 carbon atoms such as Z-methylphenyl, 3- methylphenyl, 4-ethylphenyl, 2,4-dimethylphenyl, 3,4 -dimethylphenyl, 3-sec-butylphenyl; and aralkyl of 7 to 10 carbon atoms such as benzyl, 3-phenylpropyl, and 4-phenylbutyl.

Representative substituted aryl groups which R, R may represent include halo-substituted aryl groups such as 2-fluorophenyl, 4-fluorophenyl 2- chlorophenyl, 3-chl0rophenyl, 3,4 -di-chlorophenyl, 4-trifluoromethylphenyl, 3-chloro-4-bromophenyl, 2-chloro-4-methylphenyl, 2-fluoro-4-methylphenyl, 4- chlorobenzyl, 4-fluorobenzyl, 2-(-2-fluorophenyl)ethyl; alkoxy-substituted aryl groups such as 4- methoxyphenyl, 4-ethcxyphenyl, 4-methoxy'2- methylphenyl, 4-methoxybenzyl; nitro-substituted aryl groups such as 2-nitrophenyl, 4-nitrophenyl and 4- nitrobenzyl; and aryl groups substituted with different substituents such as 2 -methoxy-4-chlorophenyl and 2- chloro-4-nitrophenyl. Substituted aryl groups preferably have 1 to 2 substituents. Preferred substituted aryl groups are halo-substituted phenyls, especially those having 1 to 2 fluorine or chlorine substituents.

Preferably R is alkyl of l to 2 carbon atoms, especially methyl.

Preferably R is phenyl or phenyl substituted with l to 2 halogens of atomic number 9 to 35 (fluorine or chlorine), trifluoromethyl groups, nitro groups, alkyl of l to 2 carbon atoms, or alkoxy of l to 2 carbon atoms.

R is preferably hydrogen or alkyl of l to 2 carbon atoms, more preferably methyl. The preferred R o p is h rq n- Representative N-chlorothio ureas of formula I are: N-chlorothio urea, N-chlorothio-N-methyl urea, N- chlorothio-N,N-dimethyl urea, N-chlorothio-N-methyl-N',N-dimethyl urea, N- chlorothio-N-methyl-N'-cyclohexyl-N-methyl urea, N-chlorothio-N-cyclopentyl-N,N'-diethyl urea, N- chlorothio-N '-methyl-N,N-dimethoxy urea, N- chlorothio-N-(2-norbornyl)-N-phenyl urea, N-

chlorothio-N-butyl-N-benzyl urea, N-chlorothio-N-(2- methylcyclohexyl)-N'-phenyl urea, N-chlorothio-N- methyl-N-(2-fluorophenyl) urea, N-chlorothio- N-methyl-N-(3,4-dichlorophenyl) urea, N-chlorothio- N-(3-trifluoromethylphenyl)N',N'-dimethyl urea, N- chlorothio-N-phenyl-N',N-dimethyl urea, N- chlorothio-N-(3,4-dichlorophenyl)-N-methoxy-N'- methyl urea, N-chlorothio-N-(3-chloro 4- bromophenyl)-N'-methoxy-N-methyl urea, N- chlorothio-N'-(4-bromophenyl)-N,N'-dimethoxy urea, N-chlorothio-N-(4 -chlorophenyl)-N',N'-dimethyl urea, N-chlorothio-N-(3,4-dichlorophenyl)-N-methyl- N'-butyl urea, N-chlorothio-N- (hexahydro-4,7-methanoinden-S-yl)-N',N'-dimethyl urea, N-chlorothio-N-(2 -fluorophenyl-N-phenyl-N- methyl urea, N-chlorothio-N-(2-fluorophenyl)-N-benzyl-N'-methyl urea, N-chlorothio-N-(2- fluorophenyl)-N-methyl-N'-propyl urea, N- chlorothio-N-(2-fluorophenyl)-N'-(2 -fluorophenyl)- N'-methyl urea, N-chlorothio-N-methyl-N'-(4- nitrophenyl)-N'-methyl urea, N-chlorothio-N-methyl- N'-(4-methoxyphenyl)-N-methyl urea, N-chlorothio- N-(3,4-dichlorophenyl)N' N'-dimethyl urea, N- chlorothio-N-(2-fluorophenyl)-N,N-dimethyl urea, N-chlorothio-.N-(4-methoxybenzyl)-N',N'-dimethyl urea, and N- chlorothio-N-(Z-methylphenyl)-N',N'-dimethyl urea.

The N-chlorothio ureas are prepared in accordance with the following reaction (1):

wherein R, R and R have the same significance as previously defined and B is an acid acceptor.

The acid acceptor is an organic base such as a pyridine compound or a trialkylamine compound. Suitable pyridine compounds are pyridine and pyridine compounds of 6 to 10 carbon atoms and of 1 to 2 alkyl groups such as 2-methylpyridine, 2-ethylpyridine, 3- methylpyridine, 3,5-dimethylpyridine, and 2- butylpyridine. Suitable trialkylamines are those wherein the alkyl group contains individually 1 to 4 carbon atoms, such astrimethylamine, triethylamine, tripropylamine and tributylamine.

Generally, commercially available sulfur dichloride of reasonable purity, e.g., greater than 90-98% purity, is suitably employed. The sulphur dichloride may contain small amounts of an inhibitor such as tributylphosphate ortriethylphosphate.

The sulfur dichloride and the urea compound are employed in substantially equimolar amounts, e.g., the molar ratio of sulfur dichloride to the urea compound generally varies from about 1.521 to 1:15, although molar ratios of sulfur dichloride to the urea compound of 1.4:1 to 1.1:1 are preferred. The molar ratios of acid acceptor to sulfur dichloride is also substantially equimolar, e.g., the molar ratio of acid acceptor to sulfur dichloride varies from about 1.2:1 to 111.2, although molar ratios ofacid' acceptor to sulfur dichloride of 1:1 to 1212 are preferred. In order to produce the N- chlorothio urea-compounds in high yield, it is essential to react the urea and sulfur dichloride in the presence ofa limited amount of free uncomplexed acid acceptor. This is suitable accomplished by the addition of the acid acceptor to a substantially equimolar mixture of the urea and the sulfur dichloride so that the moles of free acid acceptor to the total moles of urea reactant and N-chlorothio urea product is less than -0.2:1, preferably less than 0.1:1, and more preferably less than 0.05:1. In other words, during the course of the reaction between the sulfur dichloride and the urea reactant, there should be at least 5 moles of the urea reactant and the N-chlorothio urea product per mole of acid acceptor which is not complexed with hydrochloric acid. Provided that the reaction is conducted with the restricted amount of acid acceptor indicated above, the contacting of the acid acceptor with the mixture of the urea and the sulfur dichloride can be conducted by a variety of procedures. In one modification, the acid acceptor is added in increments, e.g., dropwise, in an inert diluent, if desired, to a mixture of the urea and sulfur dichloride in an inert diluent. In another modification, the acid acceptor is added continuously to a mixture of the urea and sulfur dichloride in an inert diluent.

Suitable inert diluents for the reaction include alkanes of 5 to carbon atoms, such as hexane, isooctane and decane; aromatic compounds such as benzene and chlorobenzene; oxygenated hydrocarbons such as acyclic alkyl ethers, e.g., dimethoxyethane and dibutyl ether; and cycloalkyl ethers, e.g., dioxane, tetrahydrofuran and tetrahydropyran. Other suitable diluents include nitriles such as acetonitrile and propionitrile; dialkylamide such as dimethylformamide and dialkylsulfoxides such as dimethylsulfoxide. Preferred diluents are chlorinated hydrocarbons ofl to 2 carbon atoms, such as methylene dichloride chloroform, carbon tetrachloride and ethylene dichloride. Generally, the

amount ofdiluent employed ranges from 1 to 50 moles per mole of sulfur dichloride.

The reaction is suitably conducted at a temperature between 20C. and the boiling point of the diluent. although temperatures between 0C. and 50C. are preferred. The reaction is conducted at or above atmospheric pressure.

It is appreciated, of course, that the N-chlorothio urea product of the invention is formed by the substitution ofa hydrogen substituent on an urea nitrogen atom by a sulfenyl chloride group. When the urea reactant has more than one hydrogen substituted on an urea nitrogen, a mixture of monochlorothio derivatives is therefore generally formed (unless the urea reactant is symmetrical, i.e., one R or R is hydrogen and the other R or R is the same as R). However, it has been found that when one R, R or R group is alkyl, the urea compound is preferentially sulfenylated at the nitrogen atom bearing the alkyl group.

In addition to urea reactants, the improved process of this invention is broadly applicable for the preparation of sulfenyl chloride (chlorothio) derivatives of a variety of compounds having active-hydrogen atoms substituted on nitrogen i.e., N-H functional groups. For example, Applicant's copending applications, U.S. application Ser. Nos., 251,088, now U.S. Pat. No. 3,796,712 250887 and 251,479, filed of even date, disclose the preparation of sulfenyl chloride derivatives of amino-substituted triazines, carbamates and iminoimidazolidines. This invention also constitutes an improved process for the preparation of sulfenyl chloride derivatives of N-alkylamines, N,N-dialkylamines, N-alkylanilines, amides, anilides, etc.

Examples of compounds having one or more N-H groups which can be converted to the corresponding chlorothio derivatives are disclosed in Chemical Week, pp. 43-66, April 12, 1969; Chemical Week, pp. 41-62, April 26, 1969; Frear, Pesticide lndex, 3rd Ed., 1965, College Science Publishers; and Canada Department of Agriculture, Guide to the Chemicals Used in Crop Protection, 5th Ed., 1968, the disclosures of which are hereby incorporated by reference.

The preparation of the N-chlorothio ureas is illustrated by the following examples.

EXAMPLE 1 Preparation of N-chlorothio-N-( 3 ,4-dichlorophenyl )-N ',N -dimethyl urea.

(1110. Found 5 C4- 10.7 no.7 (1 1 .6 35.4 C 54 36.1 36.4

-Continued Culc. Found H 70 3.0 3.2 N 7r 9.3 8.7

EXAMPLE2 For comparative purposes, the preparation of N- chlorothio-N-methyl-N'-3,4-dichlorophenyl urea was conducted in a series of experiments wherein the mode of addition ofthe reactants was varied. In Run 1, a mixture of 0.1 mole urea reactant (N-methyl-N'- 3,4dichlorophenyl urea) and 0.12 mole pyridine in 50 ml. of diluent (methylene dichloride) was added dropwise to 0.11 mole of sulfur dichloride in 100 ml. of diluent. In Run 2, 0.11 mole of sulfur dichloride was added dropwise to a mixture of 0.1 mole urea and 0.12 mole pyridine in 100 ml. of diluent. In Run 3, 0.12 mole pyridine was added dropwise to 0.1 mole urea and 0.11 mole sulfur dichloride in 100 ml. of diluent. In Run 4, 0.11 mole pyridine was added dropwise to 0.1 mole urea and 0.1 1 mole sulfur dichloride in 100 ml. of diluent. Runs 1-4 were all conducted at 25-30C. The yield of N-chlorothio-N-methyl-N'-(3,4-dichlorophenyl) urea was determined by converting the chlorothiourea product to an alkyldithio derivative by reaction with either. n-butyl mercaptan or isopropyl mercaptan according to the procedure described in Example 7. The reaction conditions and the yield of alkyldithio urea derivative (N-butyldithio-N-methyl-N'-3,4- dichlorophenylurea or N-isopropyldithio-N-methyl-N'- 3,4-dichlorophenylurea) and the yield of bis-(N- methyl-N-3,4-dichlorophenyl-N-ureido) sulfide (bydine hydrochloride was then filtered from the reaction mixture to give a solution of the N-chlorothio urea product in methylene chloride. The nuclear magnetic product formed by the reaction of 1 mole SCl and 2 moles urea) are tabulated in Table A.

resonance spectrum of the product showed a singlet at 3.5 ppm for the N-methyl group and a doublet at 2.95 ppm for the N-methyl group.

UTILITY The N-chlorothio urea compounds of the invention are useful intermediates for the preparation of pesticides. Useful pesticides are formed from the N- chlorothio urea compounds by more or less conventional substitution and addition reactions. Representative types of pesticides which can be prepared from the N-chlorothio urea compounds are illustrated below:

1. Preparation of Monothioperoxy Urea Compounds.

The N-chlorothio urea compounds react with alcohols to form monothioperoxy urea compounds. In terms of the N-chlorothio urea compounds represented by formula (I), the reaction can be depicted by the following equation (2).

wherein R ili and R have the same significance as previously defined and R OH is an alcohol.

The reaction is carried out by the conventional meth-' ods employed for the reaction of sulfenyl halides and hydroxylic compounds, as disclosed by E. Kuhle, Synthesis, 617 (1971 the disclosure of which is herewith incorporated by reference.

The following example illustrates the preparation of a representative monothioperoxy urea compound. In

Reactant Mole Ratios 9. Yield Bis-urea sulfide Alkyldithio Urea Run Method of Addition Urea SCI Base Mercaptan Reactant (Moles) 1 Urea/Base to SCI l 1.1 1.2 n-butyl (0.1) I 32.5 8.3 2 SC| to Urea/Base l 1.1 1.2 do. (0.1) 32.9 21.7 3 Base to Urea/SCI: l 1.1 1.2 do. (0.1) 18.8 40.1 4 Base to Urea/SCH l 1.3 1.1 isopropyl (0.14) 0 61.7

EXAMPLE 3 the example 5, the monothioperoxy urea compounds Preparation of N-chlorothio-N-methyl-N-3,4-dichlorophenyl urea.

EXAMPLE 4:

Preparation of N-chlorothio-N,N'-dimethyl urea Pyridine, 9.48 g (0.12 mole) was added dropwise to a solution of 8.8 g (0.1 mole) N,N'-dimethyl urea and 1 1.3 g (0.11 mole) sulfur dichloride at 2530C. Pyriare named as N-alkoxythio ureas.

EXAMPLE 5 Preparation of N-propoxythio-N-methyl-N'-3,4-dichlorophenyl urea.

To a solution of about 0.1mole of N-chlorothio-N- methyl-N-3,4-dichlorophenyl urea in methylene dichloride, prepared as described in Example 3, was added dropwise a solution of 6 g (0.1 mole) n-propanol and 9.5 g (0.12 mole) pyridine in 20 ml of methylene chloride at 0C. After the completion of the addition, the resulting reaction mixture was stirred in an ice bath for about 10 minutes,'washed with water, washed with sodium bicarbonate solution, dried over magnesium sulfate and evaporated under reduced pressure to give 22.6 g ofa dark oil residue. The oil residue was purified by column chromatography on silica gel (hexane/- chloroform eluent) to give the product as a white, low melting solid 25C.). Elemental analysis showed:

Cale. Found the soil surface at a dose of 100 micrograms per cm The pot was watered and placed in a greenhouse. The pot was watered intermittently and was observed for seedling emergence, health of emerging seedlings, etc.

I for a 3-week period. At the end of this period the herbiy a slmliar p F the monothloperoxlde cidal effectiveness of the urea was rated based on the Pounds tabulated Table l were P physiological observations. A 0 to 100 scale was used;

' TABLEl MONOTHIOPEROXY UREA COMPOUNDS Elemental Analysis (1 RF. MELTlNG S N RANGE. NUMBER (OM POUND C. Cnlc. Found Cale. Fountl C1110. Found 17031 N-octoxythio-N-mcthyl-N'- Oil 8.1 8.1 18.1 17.3

(3.4-dichlorophenyl) urea 17300 N-methoxythio-N-methyl-N'- 72-77 11.4 11.8 25.3 25.8

(3.4-dichlorophenyl) urea 17301 N-mcthoxythio-N-methyl-N' Oil 13.9 13.9 8.3 8.3

(Z-fluorophenyl) urea 17302 N-norbornyloxythio N-methy|- Oil 10.3 10.9 6.1 6.2

N"(2-fluorophenyl) urea 17311 N-ethoxythio-N-methybN- Oil 13.1 13.6 7.8 7.9

(2-fluorophenyl) urea 17348 N-propoxythio-N-methyl-N- Oil 10.9 11.1

(Z-fluorophenyl) urea 17349 N-isopropoxythio-N-me1hyl- Oil 10.9 11.2

N'-(2-l'luorophcnyl) urcu 17350 N-cthoxythio-N-mcthyl-N'- 6061 10.9 10.9 24.1 24.0

(3.4-dichlorophenyl) urea 17351 N'isopropoxythio-N-1r1ethyl-N'- Oil 10.4 10.7 23.0 23.2

(3.4-dichlorophcnyl) urea 1 17352 N-norbornyloxythio-N-mcthyl- Oil 8.7 9.0 19.7 19.3

N'-(3.4-dichlorophcnyl) urcu 17426 N-cyclohexyloxythio-N-methyl- 69-72 10.7 10.8 6.4 6.5

The monothioperoxy urea compounds are. in general, herbicidal in both preand post-emergence applicataions. For pre-emergence control of undesirable vegetation these ureas will be'applied in herbicidal quantities to the environment, e.g., soil infested with seeds and/or seedlings of such vegetation. Such application will inhibit the growth of or kill the seeds, germinating seeds and seedlings. For post-emergence applications the monothioperoxy urea compounds "will be applied directly to the foliage and other plant parts. Generally they are effective against weed grasses as wellas broadleaved weeds. Some may be selective with respect to type of application and/or type of weed.

Preand post-emergence herbicidal tests on the monothioperoxy urea compounds prepared above were made using the following methods:

Pre-Emergence Test An acetone solution of the test urea compound was prepared by mixing 750 mg. urea, 220 mg. of a nonionic surfactant and ml. of acetone. This solution 0 representing no phytotoxicity, 100 representing complete kill.

Pre-Emergence Test The test urea was formulated in the same manner as described in above for the pre-emergence test. The concentration of the urea in this formulation was 5,000 ppm. This formulation was uniformly sprayed on 2 replicate pots of 24-dayold plants (approximately 15 to 25 plants per pot) at a dose of 100 micrograms per cm. After the plants had dried, they were placed in a greenhouse and then watered intermittently at their bases as needed. The plants were observed periodically for phytotoxic effects and physiological and morphological responses to the treatment. After 3 weeks the herbicidal effectiveness of the urea was rated based on these observations. A 0 to 100 scale was used; 0 representing no phytotoxicity, 100 reprpesenting complete kill.

The results of these tests appear in Table 11. in Table 11, the following abbreviations are used:

O Wild Oats (Arena falua) was added to approx1mately 125 ml. of water contamw watergrass (EMU-"06mm Crusgam) mg 156 mg. of surfactant. C Crabgrass (Digimria sanguinalis) M Mustard (Brassica arvensis) Seeds of the test vegetanon were planted 1n a pot of P Pigweed (Ammmlm relmflexm) 5011 and the urea solutlon was sprayed unlformly onto L Lambsquarter (Chenopodium album) TABLE 11 Herbicidul Effectiveness Prc/Post RE NUM- COMPOUND 0 w C M P L BER 17027 N-propoxythio-N-methyl-N'- 98/100 98/100 95/80 100/100 100/100 100/100 (3.4-dichlorophenyl) urea 17031 N-octoxythio-N-methyl-N- 40/93 /100 93/93 /100 100/100 100/100 (3.4-dichlorophenyl) urea 17300 N-methoxythio-N-methyl-N'- 95/100 /100 100/85 100/100 100/100 100/100 (3.4-dichlorophenyl) urea Table llContinued Herbicidal Effectiveness Pre/Post RE NUM- COMPOUND O W C M P L BER 17301 N-methoxythio-N-methyl-N- 100/100 100/100 80/100 100/100 '100/100 100/100 (2-fluorophenyl) urea 17302 N-norbornyloxythio-N-methyl-N'- 100/100 100/100 95/100 100/100 100/100 100/100 (Z-fluorophenyl) urea 17311 N-cthoxythio-N-methyl-N- 100/100 100/100 96/65 100/100 100/100 100/100 (Z-fluorophenyl) urea 17348 N-propoxythio-N-methyl-N'- 100/100 100/100 90/70 100/100 100/100 100/100 (2-fluorop1ienyl) urea [7349' N-isopropoxythio-N-methyl- 100/100 100/100 100/90 100/100 100/100 100/100 N'-(2-fluorophenyl) urea 17350 N-ethoxythioNmethyl-N- 75/90 100/100 100/85 100/100 100/100 100/100 (3.4-dich1orophenyl) urea 17351 N-isopropoxythio-N-methyl' 90/100 100/100 100/90 100/100 100/100 100/100 N-(3,4-dichlorophenyl) urea 17352 N-norbornyloxythin-N-methyl- 45/100 100/100 95/95 100/100 100/100 100/100 N-(3.4-dichlorophenyl) urea 17426 Ncyclohexyloxythio-N-methyl* 100/100 100/100 100/100 100/100 100/100 100/100 N-(2-fluorophenyl) urea 2. Preparation of Urea 7 The N-chlorothio urea compounds react with sodium iodide to produce bis-urea disulfides of the formula wherein R, R andR have the same significance as previously defined.

The preparation of a representative bis-urea disulfide is illustrated in the following example.

EXA'MPLE6 Bis-[3-(-2-fluorophenyl)-l-methyLl-ureido]-disu1fide. [RE-17503] A solution of N-chlorothio-N-methyl-N-2- fluorophenyl urea in 150 ml'methylene dichloride was prepared from 25.2 g (0.15 mole) N-methyl-N'-2- fluorophenyl urea, 17 g (0.16 mole) sulfur dichloride and 14.2 g(0.1'8-mole) pyridine by a procedure identical to that of Example 1. To the solution of N'- chlorothio-N-methyl-N-2-fluorophenyl urea was then added dropwise asolution of 22 g (0.15 mole) sodium iodide in 45 ml water cooledto about C. in a dry ice acetone bath. After the addition was completed, the reaction mixture was stirred at 0C. for about -15 minutes. The methylene dichloride layerwass separated, washed with sodium thiosulfate solution, washedwith sodium bicarbonate solution, .washed with water, dried over magnesium sulfate and evaporated under reduced pressure to. give 20.2 g of the crude disulfide product as a yellow oil; The crude product was purified by column chromatography on silica(benzene elution) and'crystallized'from ether-hexane to'give a white solid, m.p., 87-93 C. Elemental analysis showed:

Calc. Found C 48.2 47.6 7: H 4.0 3.9 7: N 14.1 13.5 S 16.1 16.6

The urea disulfide product was effective as a herbicide for grass and broadleaved weeds.

N-chlorothi'o urea compounds of formula (1), the reaction can be depicted by the following equation (3):

wherein R, R and R have the same significance as previously defined and R SH is a mercaptan reactant.

The reaction is carried out by the conventional procedures employed for the reaction sulfenyl halides and mercaptan compounds, as disclosed by E. Kuhle, Synthesis, 6'17 (1971).

Dithio substituted ureas of formula (V) are claimed in copending application of Brown et a1, U.S. Ser. No. 88,106, filed Nov. 9, 1970, now U.S. Pat. No. 3,812,209. The preparation of representative dithio substituted ureas is illustrated in the following examples.

' EXAMPLE 7:

N-methyl-N-ethyldithio-N-(3,4 dichlorophenyl) urea.

A 9.48 g (0.12 mole) sample of pyridine was added dropwise to a slurry of 21.9 g (0.09 mole) N-methyl- N'-(3,4-dichlorophenyl) urea and 10.3 g (0.1 mole) sulfur dichloride in ml methylene dichloride at 25-30C. After the addition was completed, the reaction mixture was stirred for 20 minutes and filtered to give a solution of the chlorothio urea product in methylene dichloride. To the chlorothio urea solution was then added dropwise a solution of 6.2g ethyl mercaptan and 9.48 g pyridine in 20 ml methylene dichloride at 0C. After the addition was completed, the reaction mixture was stirred at 0C. for 10 minutes, washed with water, washed with sodium bicarbonate solution, diluted with benzene and filtered. The filtrate was dried over magnesium sulfate, filtered and evaporatedunder reduced pressure to give asolid product. The solid product was recrystallized from ether-hexane to give the urea disulfide product, m.p., l08-l09C. Elemental analysis showed:

Calc. Found S 20.6 20.2 CI 7! 22.8 23.1

TABLE 111 Elemental Analysis RE M ELTlNG N RANGE. NUM- COMPOUND C. Cale. Found Cale. Found BER 17017 NmethylN-propyldithio-N'- 79 19.7 19.6 21.9 21.9

(3.4-diehlorophenyl) urea 17024 N-mcthyl-N-methyldithio-N'- 93.5-95 21.6 21.5 20.0 24.0

(3.4-dichlorophcnyl) urea 17025 N-mcthyl-N-isopropyldithio- 103.5-106 19.7 19.5 21.9 22.6

N-(3.4-dichloropheny1) urea 17026 N-methy1-N-n-butyldithio-N- 68-685 18.9 19.0 20.9 21.0

(3,4-dichlorophenyl) urea 17109 N-methyl-N-cyclohexyldithio- 97.5-102 17.5 16.1 19.5 19.6

N '-(3 ,4-dichlorophenyl) urea 171 N-methyl-N-p-chlorobenzyldi- 98-103 157 14.2 26.1 26.2

thio-N -(3,4-dichlorophenyl) urea 171 l 1 N-methyl-N-cyclohexylthio-N- 40-42 20.4 19.2 8.9 9.2

(3,4dichlorophenyl) urea 17653 N-methyl-N-propyldithio-N'- 80-83 17.3 16.9 5.4 5.6

(3-chloro-4-bromophenyl) urea 17654 N-methyl-N-n-butyldithio-N- 64-66 16.7 15.5 5.2 5.4

(3.4-dichlorophenyl) urea 17678 N-methyl-N-methyldithio-N'- 99-998 18.7 18.6 5.9 6.0

(3.4-dichlorophenyl) urea 17825 N-methyl-N-me1hyldithio-N 011 26.0 24.3 7.7 7.4

-QQQ ZQPJ X LHEE 18320 N-Methyl-N-phenyldithio-N- 63-64 28.1 28.0 v

methylurea *Total halogen analysis **Fluorine analysis By a procedure identical to that employed for the monothioperoxy urea compounds of Example 5, the urea disulfides were tested as preand post-emergence herbicides. The results are tabulated in Table IV.

wherein R, R and R are as previously defined and R, R and R are independently R, R or R groups.

The bis-urea sulfides of formula (Vll) are claimed in copending application of Brown et al., US. Ser. No.

TABLE 1V Herhicidul Effectiveness Pre/Posi RE NUMBER COMPOUND O W C M P L 16990 N-mcthyl-N-ethyldithio-N'- /98 50/78 95/45 100/100 75/100 98/100 (3.4-dichlor0phenyl) urea 17017 N-me1hyl-Npropyldithio-N' 80/100 87/100 93/100 100/100 98/100 100/100 (3.4-dich1orophenyl) urea 17024 N-mcthyl-N-mc1hyldi1hio-N- /87 35/60 55/40 100/100 100/100 [00/100 (3.4-dich1orophcnyl) urea 17025 N-methyl-N-isopropyldithio- 30/70 50/75 87/98 100/100 95/100 95/100 N'-(3.4-diehloropheny|) urea 17026 N-mc1hy1-N-n-butyldithio-N'- /100 70/100 93/100 95/100 95/100 98/100 (3.4-dichlorophenyl) urea 17109 N-methyl-N-cycl0hexy|dilhi0- 20/35 /35 100/70 100/100 100/100 I100 N'-(3.4-dichlorophcny|) urea 17110 N-methyl-N-p-chlorobcnzyldi- 20/30 /45 100/70 100/100 100/100 100/100 1hi0-N'-(3.4-dichlorophcnyl) urea 1711 1 N-methyl-N-CyC1ohcxy1thio-N'- /100 /100 100/100 100/100 100/100 100/100 (3.4-dichlorophenyl) urea 17653 N-methyl-N-propyldithio-N- 0/50 0/55 0/70 10/90 10/100 10/100 (3,4-dichlorophenyl) urea 17654 Nmethyl-N-n-butyldithio-N'- 0/55' 0/85 0/65 0/100 0/100 0/100 (3.4dichlorophenyl) urea 17878 N-melhyl-N-methyldithiO-N- 0/100 0/85 ()/85 100/100 85/100 100/100 (3.4-dichlorophenyl) urea 17825 N-methyl-N-mcthyldithio-N'- 100/100 100/100 100/70 100/100 100/95 100/100 (Z-l'luorophcnyl) urea 4. Preparation of Bis-Urea Sulfides The N-chlorothio urea compounds react with urea compounds having at least one hydrogen substitutent on a urea nitrogen to form bis-urea sulfides. In terms the N-chlorothio urea compounds of formula (1), the

reaction can be depicted by the following equation (4): 60

88,212, filed Nov. 9, 1970, now US. Pat. No. 3,755,437.

The preparation of representative bis-urea sulfides is illustrated by the following examples.

EXAMPLE 8 [3-(2-fluorophenyl)-l-methyl-1-ureido]-[3 ,3 dimethyl-l-(3,4-dichlorophenyl)-1-ureido] sulfide. [RE-16771] H 13 about 25C. and allowed to stand overnight. The reaction mixture was thenwashed with water, washed with sodium bicarbonate, washed twice with water, dried over magnesium sulfate and evaporated to give a yellow oil. The yellow oil was crystallized from hot ethanol [3-(3,4-dichlorophenyl)-l-methy'l-l-ureido1-[3,3'- dimethyl-l -(3,4-dichlorophenyl)-l '-ureido} sulfide.

A solution of l-chlorothio-l-methyl-3-(3,4- dichlorophenyl) urea was prepared from 12 g (0.055 mole) of 1-methyl-3-(3,4-dichlorophenyl) urea, 6.28 g

1 (0.061 mole) sulfur dichloride and 5.22 g (0.066 mole) pyridine in 55 ml methylene dichloride bya procedure identical to that of Example 3. The solution of chlorothio urea was added dropwise to a slurry of 11.7 g (0.05 mole) 3,3-dimethyl-l-(3,4-dichlorophenyl) urea and 3.95 g (0.05 mole) pyridine at about 25C. and the resulting reaction mixture was stirred at about 25 C. for 2-5 2 hours. The reaction mixture was then washed with water, washed with sodium bicarbonate solution, washed with water, dried over magnesium sulfate and j evaporated under reduced pressure to give ayellowoil. The yellow oil was slurried in benzene and filtered. The filtrate was then washed through a column of silica and evaporated to give a thick oil which crystallized from ether-hexane as a white solid. Recrystallization of the. white solid from isopropanol gave the bis-urea sulfide product, m.p., l45-l49C. Elemental analysis gave:

bamate nitrogen .atom accordihg to the following equation (5):

wherein R, R and R have the same significance as previously defined and R is an organo R, R or R groups and R is hydrogen or an organo R, R or R group.

Urea carbamoyl sulfides of formula (IX) are disclosed and claimed in copending application of Brown et al, U.SZ Ser. No. 189,732, filed Nov. 15, 1971 now abandoned.

The reaction is conducted by the conventional methods generally employed for the reaction of sulfenyl halides and active proton-containing compounds. The preparation of a representative compound is illustrated in the following example:

EXAMPLE 10 (l-methyl-3-(3,4-dichlorophenyl l -ure ido)-(a naphthyl-N-methylcarbamoyl)-sulfide. [RE-17159] was added and the reaction stored overnight at room temperature. The reaction was washed with water, washed with sodium bicarbonate, dried over magnesium sulfate, and evaporated under reduced pressure to give a brown oil. The oil was slurried with other to pre- Calc. Found 40 cipitate a whlte sol1d. Recrystalllzatlon from chloro- 5 67 form/hexane gave the product, m.p. 123l24.5C. El- Cl 29.4 30.0

emental analysls showed:

' Calc. Found The bis-urea sulfides were tested as herb1c1des by the procedure used in Example 5. The results aretabulated s 7,11 7,4 in Table V. C]

TABLE V Herbicidal Effectiveness Pie/Post RE COMPOUND 0 W C M Y P L NUMBER I677] [3-(2-fluorophenyl)-l-methyl- 100/95 100/95 100/95 100/100 100/100 100/100 l-ureido]-[3.3 -dimethyl-l-(3.4- dichlorophenyl)-l-urcido]- sulfide 18068 {3-(3.4-dichlorophcnyU-l 98/100 100/100 98/73 100/100 100/100 100/100 n1ethyl-l-ureido]-[ 3,3-dimethy l-(3.4-dichlorophenyl)-lurcidol-sulfidc 5. Preparation of Urea Carbamoyl Sulfides The N-chlorothio urea compounds react with carbamates have at least one hydrogen substituent on a car- The urea-carbamoyl sulfide product was tested as a herbicide by the procedure employed in Example 5. The results are tabulated in Table Vl.

TABLE V1 E-lerbicidal Effectiveness Pre/Post RE COMPOUND o w C M P L NUMBER 171559 [1methyl-3-(3,4-dichloro- 20/45 25/70 80/65 100/100 100/100 100/100 phenyl)-1-ureido]-(a-naphthyl- N-methylcarbamoyl) sulfide 6. Preparation of Aminothio Ureas The N-chlorothio urea compounds react with primary and secondary amines and anilines to produce R 0 g 1 F am1noth1o subst1tuted ureas accordmg to the .ollowmg g l( equat1on (6):

R R R2 R wherein R, R and R have the same significance as previously defined and R is an organo R, R or R group and R is hydrogen or R.

The preparation of a representative aminothio urea is illustrated by the following example:

EXAMPLE 11 N-( 3 ,4-dichlorophenylaminothio )-N-methyl- N'-(3,4-dichlorophenyl) urea.

showed:

Cale. Found The product was tested as a pre and post-emergence herbicide as described heretofore and found to be effective for the control ofgrass and broad-leaved weeds.

7. Addition to Olefins The N-chlorothio urea compounds add to olefms to form the corresponding 1,2-addition product as depicted in the following equation for addition to cyclohexane.

wherein R, R and R have the same significance as previously defined.

The invention is conducted by conventional procedures, e.g., by the contacting of an olefin and the N- chlorothio urea in an inert solvent at moderate temperatures, e.g., 0 to 50C.

The products resulting from the addition of an N- chlorothio urea to cycloalkenes of 5 to 12 carbon atoms or norbornene are known and are disclosed in U.S. Ser. No. 54,855 of Kobzina et al filed July 14, 1970, now U.S. Pat. No. 711,530 common assignee. The disclosure of U.S. Ser. No. 54,855 is herewith incorporated by reference.

The preparation of a representative olefin addition product is illustrated by the following example:

EXAMPLE l2 N-methyl-N-(2-chlorocyclohexylthio )-N (2-fluorophenyl) urea.

A 569 g (7.2 mole) sample of pyridine was added over a period of 18 minutes to a mixture of 1,008 g (6 mole) of N-methyl-N -(Z-fluorophenyl) urea and 680 g (6.6 mole) sulfur dichloride in 6 ml methylene dichlo ride cooled to below 30C. with a dry ice/acetone bath. After the addition was completed, the pyridine hydrochloride salt was filtered. A 443 g (5.4 mole) sample of cyclohexane was then added to the resulting filtrate cooled to 0C. with a dry ice/acetone bath. After 15 minutes of stirring, the resulting reaction mixture was washed with water, sodium bicarbonate solution, dried over magnesium sulfate and evaporated under reduced pressure to give 1700 g of urea product as a yellow oil.

8. Additional N-Chlorothio Urea Derivatives The reaction of the N-chlorothio areas with N alkylanilides, thio-substituted carboxylic acid esters, and compounds having two active-hydrogen functional groups such as alkanes having two mercapto groups, two hydroxyl group, two amino groups, or two different amino, mercapto or hydroxyl groups, is illustrated by the following examples:

urea (01 mole) in ml methylene chloride was prepared in a manner identical to Example 3. 3,4-

3,857,883 17 1s Dichlorophenyl-n-propanilide, 19.6 g (0.09 mole) and with ether and hexane to give the product. m.p. pyridine, 7.9 g (0.1 mole) were added to the chlorothio 92.5-95C. Elemental analysis showed: urea and the reaction stirred overnight. The resulting mixture was washed with water, washed with sodium bicarbonate, dried over magnesium sulfate, and evapo- 5 Cale" 111111111 rated under reduced pressure to give a gray solid. Recrystallization from chloroform hexane gave the product. m.p. 149-152C. Elemental analysis showed: 8'0

The product was effective as a pre-and post- Calc' Fmmd emergence herbicide for grass and broad-leaved weeds. s /1 6.9 7.0 CI "/1 30.4 30.5 EXAMPLE 15 Preparation of The product was tested as a preand post-emergence N-(2-carbomethoxyethyldithio)-N- herbicide as described heretofore and found to be efmethyl-N'-(3,4-dichlorophenyl) urea. [RE-17353] fective for the control of grass and broad-leaved weeds. N chlorothio N methyl N/ (34 dichlorophenyl) urea (0.1 mole) in 100 ml methylene chloride was preared in a manner identical to Exam le 3. F F l Y li lethyl-3-mercaptopropionate (0.09 mole) an d pyri- The 1,2-ethane-b1s-urea d1sulf1de of the formula: dine, 79 g (01 mole) dissolved in 10 m] methylene chloride was added to the chlorothio urea at 0C. The reaction was stirred 10 minutes after the addition was F completed and the mixture was washed with water, I 0 washed with sodium bicarbonate, dried over magneil sium sulfate and evaporated under reduced pressure to I yield an oil. Chromatography over silica gel (benzene 3 eluent) yielded the product, a dark gray oil. Elemental analysis showed:

was prepared as follows:

N-chlorothio-N-methyl-N-2-fluorophenyl urea (0.1

mole) in 100 ml methylene chloride was prepared in a Calc. Found manner identical to Example 3. 1,2-ethanedithiol, 4.2 S r/ n 3 7 7 g (0.045 mole) and pyridine, 7.9 g (0.1 mole) dissolved Cl in 20 ml methylene chloride were added to the chlorothio urea at 0C. and the mixture stirred ten minutes following the addition. The reaction was then washed By a similar procedure the urea compounds tabuwith water, washed with sodium bicarbonate, dried lated in Table Vll were prepared. The pre and postover magnesium sulfate, and evaporated under reduced emergence herbicidal test results for these compounds pressure to yield a white solid. The solidwas washed are tabulated in Table Vlll.

TABLE VII Elemental Analysis RE MELTING S Halogen NBlll- COMPOUND RANGE "C. Calc. Found Calc. Found 17353 N-(2-carbomethoxyethyldi- Oil 1 17.3 17.2 119.2 19.6 (C1) thio)-N-methylN-(3,4-dichlorophenyl) urea 17030 N-(carbomethoxymethyldi- 94.5-95.5 18.0 17.6 20.0 20.0 (C1) thio)-N-methyl-N' (3,4-dichlorophenyl) urea 17652 N-(carbethoxymethyldithio)- 82-83 17.3 16.6 19.2 18.5 (C1) N-methyl-N'-(3,4-dichlorophenyl) urea 17527 N-(carbomethoxymethyldi- 96-975 16.0 15.7 5.0 5.1 (Br,Cl)

thio)-N-methyl-N'-(3- chloro-4-bro'mophenyl) urea 17374 N-(2-carbomethoxyethyldi- 51-52.5 8.8 9.0 (Nitrogen) thio)-N-methyl-N-(2- fluorophenyl) urea 17424 Nicarbomethoxymcthyldi- Oil 21.1 21.2 6.3 6.2-(F) thio)-N-methyl-N-(2-fluorophenyl) urea 17679 N-(Z-carbomethoxyethyldi- Oil 15.5 15.2 4.8 4.8 (Br,Cl)

thio)-N-methyl-N'-(3-ch1oro- 4-bromophenyl) urea 17680 N-(carbethoxymethyldithio)- 88.5-91.5 15.5 15.4 4.8 4.9 (Br,Cl)

N-methyl-N'-(3-chloro-4- bromophenyl) urea TABLE Vlll Herbicidal Effectiveness Pre/Post RE COMPOUND O W C M P 1 NUMBER 17353 N-(2-carbomethoxyethy1dithio) 45/70 100/75 90/85 100/100 100/100 100/100 N-metliyl-N'-(3,4-dichlorophenyl)urea 17030 N-(curbomethoxymethyldithio) 95/99 1110/98 100/75 100/100 100/100 100/100 N-methyl-N'-(3,4-dichlorophenyl) urea 17652 N-(cflrbcthoxymethyldithio)- 100/95 1011/100 100/100 100/100 100/100 100/100 N-mcthy1-N'-(3,4-dichlorophenyllurea 17527 N-(carbomethoxymethyldithio)- 55/95 80/95 85/100 90/100 100/100 100/100 N-methyl-N'-(3-chloro-4-bromo phenyl)urea 17374 N-(Learbomethoxyethyldithio)- 100/100 100/95 100/90 100/100 100/100 100/100 N-methy1-N'-(Z-fluorophenyl) urea 17424 N-(carbomethoxymethyldithio)- 95/100 100/100 100/100 100/100 100/100 100/100 N-methyl-N'-(2-fluorophenyl) urea 17679 N-1Z-carbomethoxyethyldithiol- 40/95 1110/60 100/80 100/100 100/100 100/100 N-methyl-N'-(3-chloro-4-bromophenyl) urea 17680 N-(carbethoxymethyldithi/-N- 60/100 100/75 100/100 100/100 100/100 100/100 methyl-N 3-ch10ro-4-hromophenyl) urea O Wild Oats (Arena fulua) W Watergrass (Et'kiltm'hlnu crurrnlli) C Cruhgrasx (Digiluriu .runguinulixl M Mustard (Hrusrit'u un'enrix) l. Lunihsqnilrlcr ((Vu-rmpwlimn album) 1 claim:

1. 1n the process for producing an N-chlorothio urea derivative which comprises reacting substantially equimolar amounts of a urea reactant of the formula wherein R, R and R independently are hydrogen, alkyl of 1 to 6 carbon atoms, alkoxy of l to 4 carbon atoms, aryl of 6 to 10 carbon atoms, aryl of6 to 10 carbon atoms substituted with 1 to 4 halogen atoms of atomic number 9 to 35, trichlormethyl, trifluoromethyl, nitro groups or alkoxy groups individually of 1 to 4 carbon atoms, and sulfur dichloride in the presence of an organic base acceptor to complex the hydrochloric acid formed in the reaction, the improvement which comprises maintaining during reaction the moles of uncomplexed acceptor to the total moles of urea reactant and N-chlorothio urea product at a ratio of less than 0.2:] by the controlled addition of the acceptor to a mixture of the urea reactant and sulfur dichloride in an inert diluent.

2. The process of claim 1 wherein the ratio of unreacted acceptor to the total moles of urea reactant and N-chlorothio urea product is less than 0. 1:1.

3. The process of claim 1 wherein the organic base acceptor is pyridine.

4. The process of claim 3 wherein the temperature is between 0C. and 50C.

5. The process of claim 4 wherein the ratio of unreacted acceptor to the total moles of urea reactant and N-chlorothio urea product is less than 0.05:1.

6. The process of claim 1 wherein R is alkyl of 1 to 2 carbon atoms.

7. The process of claim 6 wherein R is hydrogen and R is phenyl or phenyl substituted with 1 to 2 fluorine or chlorine groups.

8. The process of claim 7 wherein R is methyl, R is 2fluoropheny1 and R is hydrogen.

9. The process of claim 7 wherein R is methyl, R is 3,4-dich1orophenyl and R is hydrogen. 

1. IN THE PROCESS FOR PRODUCING AN N-CHLOROTHIO UREA DERIVATIVE WHICH COMPRISES REACTING SUBSTANTIALLY EQUIMOLAR AMOUNTS OF A UREA REACTANT OF THE FORMULA
 2. The process of claim 1 wherein the ratio of unreacted acceptor to the total moles of urea reactant and N-chlorothio urea product is less than 0.1:1.
 3. The process of claim 1 wherein the organic base acceptor is pyridine.
 4. The process of claim 3 wherein the temperature is between 0*C. and 50*C.
 5. The process of claim 4 wherein the ratio of unreacted acceptor to the total moles of urea reactant and N-chlorothio urea product is less than 0.05:1.
 6. The process of claim 1 wherein R is alkyl of 1 to 2 carbon atoms.
 7. The process of claim 6 wherein R2 is hydrogen and R1 is phenyl or phenyl substituted with 1 to 2 fluorine or chlorine groups.
 8. The process of claim 7 wherein R is methyl, R1 is 2-fluorophenyl and R2 is hydrogen.
 9. The process of claim 7 wherein R is methyl, R1 is 3,4-dichlorophenyl and R2 is hydrogen. 